Lithium orthophosphate glasses, corresponding glass-ceramics and lithium ion-conducting NZP glass ceramics

ABSTRACT

A lithium-ion conductive glass-ceramic article has a crystalline component characterized by the formula MA2(XO4)3, where M represents one or more monovalent or divalent cations selected from Li, Na and Zn, A represents one or more trivalent, tetravalent or pentavalent cations selected from Al, Cr, Fe, Ga, Si, Ti, Ge, V and Nb, and X represents P cations which may be partially substituted by B cations.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority under 35 U.S.C. § 119 of U.S. Provisional Application Ser. No. 61/870,995 filed on Aug. 28, 2013, the entire content of which is hereby incorporated by reference.

BACKGROUND Field

The present disclosure relates generally to lithium ion-conductive materials and more specifically to a glass-ceramic process for forming dense, lithium ion-conducting membranes.

Technical Background

Solid electrolytes, also known as fast ion conductors, can be used in energy storage devices such as solid oxide fuel cells and lithium-ion batteries. The solid electrolyte permits movement of ions without the need for a liquid or soft membrane separating the electrodes. In a lithium-ion battery, for example, lithium ions move from a negative electrode to a positive electrode during discharge (and back when charging) via the solid electrolyte. The solid electrolyte can conduct lithium ions through vacancies in the electrolyte crystal lattice. The solid electrolyte can also provide a hermetic barrier between the anode and the cathode in order to prevent the anode and cathode from sharing a common electrolyte solution.

Important to the development of Li-ion batteries is the availability of dense, solid, ion-conductive electrolyte membranes. A challenge in the formation of such membranes via traditional ceramic routes is the inability to sinter suitable starting materials to sufficient density to form a membrane that is hermetic while providing the requisite conductivity and economy.

In view of the foregoing, it would be desirable to develop an economical process for forming solid, lithium ion-conductive membranes.

BRIEF SUMMARY

In accordance with embodiments of the present disclosure, lithium ion-conductive, lithium titanium metal phosphate glass-ceramic membranes having an NZP crystal phase as the predominate crystal phase are formed by quenching and heat treating a molten glass having the corresponding composition.

A glass can be formed, for example, by roller quenching a glass from the melt. The molten glass and the resulting glass article can have a composition comprising, in mole percent, 5-28% Li₂O, 14-37% TiO₂ and 32-48% P₂O₅. The composition further comprises one or more of Al₂O₃, Cr₂O₃, Fe₂O₃, Ga₂O₃, SiO₂, GeO₂, V₂O₅, Nb₂O₀, Na₂O, ZnO and B₂O₃.

In embodiments, the glass composition satisfies at least one relationship (i)-(iii), where (i) the composition comprises at least two oxides selected from the group consisting of >0-13% Al₂O₃, >0-13% Fe₂O₃ and >0-13% Nb₂O₅; (ii) the composition comprises at least two oxides selected from the group consisting of >0-10% Cr₂O₃, >0-5% SiO₂ and >0-25% GeO₂; and (iii) the composition comprises at least three oxides selected from the group consisting of >0-13% Al₂O₃, >0-13% Fe₂O₃, >0-13% Nb₂O₅, >0-10% Cr₂O₃, >0-5% SiO₂ and >0-25% GeO₂.

A glass-ceramic article may be formed by heat treating the glass. The glass-ceramic article has a majority crystalline component characterized by the formula M_(y)A₂(XO₄)₃ (0.1≤y≤2.2), where M represents one or more monovalent or divalent cations selected from the group consisting of Li, Na and Zn, A represents one or more trivalent, tetravalent or pentavalent cations selected from the group consisting of Al, Cr, Fe, Ga, Si, Ti, Ge, V and Nb, and X represents P cations which may be partially substituted by B cations. The glass-ceramic may be further characterized by at least one relationship (i)-(iii), where (i) A represents two or more cations selected from the group consisting of Al, Fe and Nb; (ii) A represents two or more cations selected from the group consisting of Cr, Si and Ge; and (iii) A represents three or more cations selected from the group consisting of Al, Fe, Nb, Cr, Si and Ge. Glass-ceramics containing the aforementioned NZP phase may be characterized by a high lithium ion conductivity.

Additional features and advantages of the subject matter of the present disclosure will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the subject matter of the present disclosure as described herein, including the detailed description which follows, the claims, as well as the appended drawings.

It is to be understood that both the foregoing general description and the following detailed description present embodiments of the subject matter of the present disclosure, and are intended to provide an overview or framework for understanding the nature and character of the subject matter of the present disclosure as it is claimed. The accompanying drawings are included to provide a further understanding of the subject matter of the present disclosure, and are incorporated into and constitute a part of this specification. The drawings illustrate various embodiments of the subject matter of the present disclosure and together with the description serve to explain the principles and operations of the subject matter of the present disclosure. Additionally, the drawings and descriptions are meant to be merely illustrative, and are not intended to limit the scope of the claims in any manner.

BRIEF DESCRIPTION OF THE DRAWINGS

The following detailed description of specific embodiments of the present disclosure can be best understood when read in conjunction with the following drawings, where like structure is indicated with like reference numerals and in which:

FIG. 1 is a compositional landscape for Ti, Cr and Ge-containing materials showing glass forming regions and ionic conductivities;

FIG. 2 is a DSC scan for a glass composition according to one embodiment;

FIG. 3 is a DSC scan for a glass composition according to a further embodiment;

FIG. 4 is an XRD scan for a glass-ceramic according to one embodiment;

FIG. 5 is an SEM micrograph of the glass-ceramic of FIG. 4;

FIG. 6 is a DSC scan for a glass composition according to a further embodiment;

FIG. 7 is an XRD scan for a glass-ceramic according to one embodiment; and

FIG. 8 is a plot of weight loss versus time for example glass-ceramic compositions when submerged in deionized water.

DETAILED DESCRIPTION

Reference will now be made in greater detail to various embodiments of the subject matter of the present disclosure, some embodiments of which are illustrated in the accompanying drawings. The same reference numerals will be used throughout the drawings to refer to the same or similar parts.

Disclosed are precursor glasses and NASICON-type (i.e., NZP-type) materials that are formed via a glass-ceramic route. According to various embodiments, vitreous domains in Li₂O—TiO₂—P₂O₅ are disclosed, further comprising one or more of Al₂O₃, Cr₂O₃, Fe₂O₃, Ga₂O₃, SiO₂, GeO₂, V₂O₅, Nb₂O₅, Na₂O, ZnO and B₂O₃.

The glasses are obtained by melting of a mixture of Li₂CO₃(s) and/or LiH₂PO₄(s), TiO₂(s), H₃PO₄(aq) and an oxide, carbonate or phosphate of one or more additional metal(s). The dry batch ingredients can be turbula milled, for example, prior to the addition of aqueous phosphoric acid to form a slurry. The slurry is calcined.

The calcination time and temperature may range from 1-12 h and 300-500° C., respectively. An example calcination time is 6 h and an example calcination temperature is 400° C. Following calcination, the batch is placed in a melting furnace. Calcined batches are melted at 1400-1600° C. (e.g., 1500° C.) and then roller quenched to form thin sheets. Molten material can be quenched from the melt temperature to less than 600° C. at a quench rate of from 40° C./min to 200° C./min (e.g., 80 or 100° C./min). The molten material can be roller quenched on a stainless steel substrate.

The glass sheets may have areal dimensions of several square centimeters, though the process may be scaled to larger area sheets. The melt can be quenched and rolled into sheets having a maximum thickness of 2 mm. In embodiments, the thickness of the glass sheets was about 0.5 to 1 mm.

The roller-quenched glass is then heat treated to nucleate and grow the crystalline phase. The heat treatment can be performed under ambient conditions. A heating rate to a nucleation temperature can range from 1° C./min to 20° C./min, e.g., 1, 2, 5, 10 or 20° C./min. A heating rate to a crystal growth temperature can range from 1° C./min to 20° C./min, e.g., 1, 2, 5, 10 or 20° C./min. Depending on the composition of the batch, the nucleation temperature can range from 500° C. to 700° C. and the crystal growth temperature can range from 800° C. to 900° C. A nucleation time and a crystal growth time can range from 0 to 2 h and 0.25 h to 72 h, respectively.

When the glass is subjected to a heat treatment above its crystallization temperature (T_(x)), the dominant phase of the resultant glass-ceramic has the rhombohedral NZP structure. In embodiments, the crystal growth temperature is at least 50° C. greater, e.g., at least 100° C., 200° C., 300° C. or 350° C. greater than the crystallization temperature (T_(x)) of the composition.

In the NASICON framework, represented by the formula M(1)M(2)A₂(XO₄)₃, the crystal structure comprises a three-dimensional network of XO₄ tetrahedra sharing corners with AO₆ octahedra. The M(1) sites are surrounded by six oxygen atoms and located at an inversion center. The M(2) sites are symmetrically-distributed around a three-fold axis with ten-fold oxygen coordination.

Without wishing to be bound by theory, the M(1) and M(2) sites are principally occupied by one or more alkali metal ions such as Li or Na, though the alkali metal ions may be substituted partly by Zn or a vacancy. The symbol A represents two or more (e.g., three or more) multivalent metal ions, e.g., Al, Cr, Fe, Ga, Si, Ti, Ge, V and Nb, and the symbol X is principally phosphorus (P) though the phosphorus may be substituted partially by B.

The resulting glass-ceramic membrane can have an average thickness of less than 2 mm, e.g., from 0.5 to 1 mm. In embodiments, the glass-ceramic can have an average thickness of less than 200 microns, where the constituent crystalline material can have an average grain size of less than 10 um, e.g., less than 1 um. Self-supporting glass-ceramic membranes as thin as 100 microns can be formed.

The glass-ceramic article may contain less than 5 vol. % retained glassy phase. In embodiments, the glass-ceramic article is entirely crystalline or contains at most 1 vol. % or 2 vol. % retained glass. In further embodiments, the glass-ceramic includes a NZP-type crystal as the majority crystalline phase. By majority crystalline phase, it is meant that the glass-ceramic can include at least 70 vol. % (e.g., at least 70, 75, 80, 85, 90 or 95 vol. %) NZP phase. The glass-ceramic may contain an NZP-type crystalline phase as the sole crystal phase.

The composition of the batch of raw materials can correspond directly to the stoichiometry of the crystal phase that is desired. Thus the disclosed glass compositions and the disclosed glass-ceramic compositions may each include, in mol. %: 5-28% Li₂O, 14-37% TiO₂, and 32-48% P₂O₅ with one or more of the following: 0-13% Al₂O₃, 0-10% Cr₂O₃, 0-13% Fe₂O₃, 0-10% Ga₂O₃, 0-5% SiO₂, 0-25% GeO₂, 0-7% V₂O₅, 0-13% Nb₂O₅, 0-17% Na₂O, 0-17% ZnO and 0-6% B₂O₃.

The glass compositions, in example embodiments, comprise 5-28% Li₂O, 14-37% TiO₂, and 32-48% P₂O₅, and further comprising at least one relationship (i)-(iii), wherein (i) the composition comprises at least two oxides selected from the group consisting of >0-13% Al₂O₃, >0-13% Fe₂O₃ and >0-13% Nb₂O₅, (ii) the composition comprises at least two oxides selected from the group consisting of >0-10% Cr₂O₃, >0-5% SiO₂ and >0-25% GeO₂; and (iii) the composition comprises at least three oxides selected from the group consisting of >0-13% Al₂O₃, >0-13% Fe₂O₃; >0-13% Nb₂O₅, >0-10% Cr₂O₃, >0-5% SiO₂ and >0-25% GeO₂.

The composition of the glass may correspond stoichiometrically to the NZP crystal phase. In related embodiments, the composition of the glass may be non-stoichiometric with respect to the NZP crystal phase. For example, the glass composition may be up to 10 mol. % deficient or may contain up to 10 mol. % excess of one or more constituents. A glass may be prepared, for instance, with 5% or even 10% excess phosphorus.

The resulting glass-ceramic has a crystalline component characterized by the formula M_(y)A₂(XO₄)₃ (0.1≤y≤2.2), where M represents one or more monovalent or divalent cations selected from the group consisting of Li, Na and Zn, A represents two or more trivalent, tetravalent or pentavalent cations selected from the group consisting of Al, Cr, Fe, Ga, Si, Ti, Ge, V and Nb, and X represents P cations which may be partially substituted by B cations, and further comprising at least one relationship (i)-(iii), where (i) A represents two or more cations selected from the group consisting of Al, Fe and Nb; (ii) A represents two or more cations selected from the group consisting of Cr, Si and Ge; and (iii) A represents three or more cations selected from the group consisting of Al, Fe, Nb, Cr, Si and Ge. In example glass-ceramic compositions, M is Li and the subscript y can range from 1.2 to 2.2.

In embodiments, A may represent two or more trivalent, tetravalent or pentavalent cations selected from the group consisting of Al, Cr, Fe, Ga, Si, Ti, Ge, V and Nb. In further embodiments, A may represent three or more trivalent, tetravalent or pentavalent cations selected from the group consisting of Al, Cr, Fe, Ga, Si, Ti, Ge, V and Nb. In still further embodiments, A may represent four or more trivalent, tetravalent or pentavalent cations selected from the group consisting of Al, Cr, Fe, Ga, Si, Ti, Ge, V and Nb.

It will be appreciated that in the idealized stoichiometry, M_(y)A₂(XO₄)₃ (0.1≤y≤2.2), the elemental constituents may be located on alternate sites to those described above. For example, in a Li_(1.3)Nb_(0.45)Al_(0.45)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) glass ceramic, the aluminum (Al) may be located on an X site or on an interstitial site within the crystalline matrix.

Example glass stoichiometries are summarized in Table 1, where the constituent compositions are given in molar %.

The Li₂O content (in mol. %) of the disclosed glass and glass-ceramic compositions can range from 5-28%. For example, the compositions may include from 10-22% or from 12-20% Li₂O, e.g., 10, 12, 14, 16, 18, 20 or 22% Li₂O. The amount of TiO₂ (in mol. %) of the disclosed glass and glass-ceramic compositions can range from 14-37%. In embodiments, the composition include at least 18 mol. % TiO₂. For example, the compositions may include from 18-36% or from 20-30% TiO₂, e.g., 20, 22, 24, 26, 28 or 30% TiO₂. The amount of P₂O₅ (in mol. %) of the disclosed glass and glass-ceramic compositions can range from 32-48%. For example, the compositions may include from 36-46% or from 38-42% P₂O₅, e.g., 36, 38, 40, 42, 44 or 46% P₂O₅.

The disclosed glass and glass-ceramic compositions may optionally include Al₂O₃ or Fe₂O₃. The Al₂O₃ or Fe₂O₃ content (in mol. %) can independently range from 0-13%. For example, the compositions may include from 4-10% or from 6-8% Al₂O₃, e.g., 4, 6 or 8% Al₂O₃. The compositions may include from 2-12%, 2-6% or from 4-10% Fe₂O₃, e.g., 2, 4, 6, 8 or 10% Fe₂O₃.

The disclosed glass and glass-ceramic compositions may optionally include Cr₂O₃ or Ga₂O₃. The Cr₂O₃ or Ga₂O₃ content (in mol. %) can independently range from 0-10%. For example, the Cr₂O₃ may range from 1-8% or from 4-6%, e.g., 1, 2, 4, 6, or 8% Cr₂O₃. The Ga₂O₃ content may range from 4-8% or from 6-8%, for example.

The disclosed compositions may optionally include from 0-5 mol. % SiO₂, e.g., from 2-4 mol. % SiO₂.

The disclosed compositions may optionally include from 0-25 mol. % GeO₂. For example, the compositions may include from 4-20%, 6-10% or from 10-15% GeO₂, e.g., 4, 6, 8, 10, 12, 14 or 16% GeO₂.

The disclosed compositions may optionally include from 0-7 mol. % V₂O₅, e.g., from 2-6% or from 4-6% V₂O₅.

The disclosed compositions may optionally include from 0-13 mol. % Nb₂O₅. For example, the compositions may include from 4-10% or from 4-8% Nb₂O₅, e.g., 4, 6, 8 or 10% Nb₂O₅.

The disclosed compositions may optionally include Na₂O or ZnO. The Na₂O or ZnO content (in mol. %) can independently range from 0-17%. The compositions may include, for example, 4-10% or 6-8% ZnO, e.g., 4, 6, 8 or 10% ZnO.

The disclosed compositions may optionally include from 0-6 mol. % B₂O₃, e.g., 1-6% or 1-4% B₂O₃.

TABLE 1 Stoichiometry and composition of example lithium ion-conducting materials. Stoichiometry Li₂O TiO₂ P₂O₅ ZnO Al₂O₃ Cr₂O₃ Fe₂O₃ SiO₂ GeO₂ V₂O₅ Nb₂O₅ B₂O₃ Zn_(0.25)Li_(0.5)Fe_(0.7)Nb_(0.7)Ti_(0.6)(PO₄)₃ 7.58 18.18 45.45 7.58 — — 10.61  — — — 10.61  — LiFe_(0.7)Nb_(0.7)Ti_(0.6)(PO₄)₃ 15.15 18.18 45.45 — — — 10.61  — — — 10.61  — Zn_(0.15)LiFe_(0.3)Nb_(0.3)Al_(0.3)Ti_(1.1)(PO₄)₃ 13.51 29.73 40.54 4.05 4.05 — 4.05 — — — 4.05 — Zn_(0.25)Li_(0.8)Fe_(0.3)Nb_(0.3)Al_(0.3)Ti_(1.1)(PO₄)₃ 10.81 29.73 40.54 6.76 4.05 — 4.05 — — — 4.05 — Li_(1.3)Nb_(0.3)Al_(0.6)Ti_(1.1)(PO₄)₃ 17.57 29.73 40.54 — 8.11 — — — — — 4.05 — Zn_(0.15)LiNb_(0.3)Al_(0.6)Ti_(1.1)(PO₄)₃ 13.51 29.73 40.54 4.05 8.11 — — — — — 4.05 — Zn_(0.25)Li_(0.8)Nb_(0.3)Al_(0.6)Ti_(1.1)(PO₄)₃ 10.81 29.73 40.54 6.76 8.11 — — — — — 4.05 — Zn_(0.4)LiAl_(0.8)Ti_(1.2)(PO₄)₃ 12.82 28.21 38.46 10.26  10.26  — — — — — — — Zn_(0.3)LiCr_(0.3)Al_(0.3)Ti_(1.4)(PO₄)₃ 13.51 29.73 40.54 8.11 4.05 4.05 — — — — — — Li_(1.6)Ga_(0.6)Ti_(1.4)(PO₄)₃ 20.00 35.00 37.50 — — — — — — — — — Zn_(0.3)Li_(1.3)Fe_(0.3)Al_(0.6)Ti_(1.1)(PO₄)₃ 16.25 27.50 37.50 7.50 7.50 — 3.75 — — — — — Li_(1.3)Cr_(0.3)Nb_(0.3)Al_(0.3)Ti_(1.1)(PO₄)₃ 17.57 29.73 40.54 — 4.05 4.05 — — — — 4.05 — LiNb_(0.45)Al_(0.45)Ti_(1.1)(PO₄)₃ 14.08 30.99 42.25 — 6.34 — — — — — 6.34 — Li_(0.95)Nb_(0.4)Al_(0.35)Ti_(1.25)(PO₄)₃ 13.19 34.72 41.67 — 4.86 — — — — — 5.56 — LiNb_(0.6)Al_(0.6)Ti_(0.8)(PO₄)₃ 14.71 23.53 44.12 — 8.82 — — — — — 8.82 — Li_(1.6)Fe_(0.3)Nb_(0.3)Al_(0.6)Ti_(0.8)(PO₄)₃ 21.62 21.62 40.54 — 8.11 — 4.05 — — — 4.05 — Li_(1.3)V_(0.3)Al_(0.6)Ti_(1.1)(PO₄)₃ 17.57 29.73 40.54 — 8.11 — — — — 4.05 — — Li_(0.7)V_(0.3)Nb_(0.3)Al_(0.3)Ti_(1.1)(PO₄)₃ 10.29 32.35 44.12 — 4.41 — — — — 4.41 4.41 — Li_(1.3)Nb_(0.45)Al_(0.45)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) (example 1) 17.57 29.73 38.51 — 6.08 — — — — — 6.08 2.03 Li_(1.6)Nb_(0.45)Al_(0.45)Ti_(1.1)(PO₄)_(2.7)(BO₄)_(0.3) 20.78 28.57 35.06 — 5.84 — — — — — 5.84 3.90 Li_(1.3)Cr_(0.3)Ge_(0.6)Ti_(1.1)(PO₄)₃ (example 2) 16.25 27.50 37.50 — — 3.75 — — 15.00 — — — Li_(1.3)Cr_(0.3)Ge_(0.9)Ti_(0.8)(PO₄)₃ 16.25 20.00 37.50 — — 3.75 — — 22.50 — — — Li_(1.4)Fe_(0.3)Nb_(0.3)Al_(0.4)Ti_(1.0)(PO₄)₃ 18.92 27.03 40.54 — 5.41 — 4.05 — — — 4.05 — Li_(1.4)Fe_(0.4)Nb_(0.4)Al_(0.4)Ti_(0.8)(PO₄)₃ 19.44 22.22 41.67 — 5.56 — 5.56 — — — 5.56 — Li_(1.6)Cr_(0.6)Ge_(0.6)Ti_(0.8)(PO₄)₃ (example 3) 20.00 20.00 37.50 — — 7.50 — — 15.00 — — — Li_(1.6)Cr_(0.3)Ge_(0.6)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) (example 4) 19.28 26.51 34.34 — — 3.61 — — 14.46 — — 1.81 Li_(1.4)Cr_(0.4)Ge_(0.4)Ti_(1.2)(PO₄)₃ 17.50 30.00 37.50 — — 5.00 — — 10.00 — — — Li_(1.6)Cr_(0.3)Al_(0.3)Ge_(0.3)Ti_(1.1)(PO₄)₃ 20.00 27.50 37.50 — 3.75 3.75 — — 7.50 — — — LiNb_(0.45)Al_(0.45)Ge_(0.2)Ti_(0.9)(PO₄)₃ 14.08 25.35 42.25 — 6.34 — — — 5.63 — 6.34 — Li_(1.9)Cr_(0.6)Ge_(0.6)Ti_(0.8)(PO₄)_(2.85)(BO₄)_(0.15) 22.89 19.28 34.34 — — 7.23 — — 14.46 — — 1.81 Li_(1.6)Cr_(0.6)Si_(0.1)Ti_(1.3)(PO₄)₃ 20.00 32.50 37.50 — — 7.50 —  2.50 — — — — Li_(1.9)Cr_(0.6)Si_(0.1)Ti_(1.3)(PO₄)_(2.85)(BO₄)_(0.15) 22.89 31.33 34.34 — — 7.23 —  2.41 — — — 1.81 Li_(1.9)Cr_(0.3)Al_(0.3)Ge_(0.3)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) 22.89 26.51 34.34 — 3.61 3.61 — — 7.23 — — 1.81 Li_(1.8)Cr_(0.4)Al_(0.4)Ge_(0.3)Ti_(0.9)(PO₄)₃ 22.50 22.50 37.50 — 5.00 5.00 — — 7.50 — — — Li_(2.1)Cr_(0.4)Al_(0.4)Ge_(0.3)Ti_(0.9)(PO₄)_(2.85)(BO₄)_(0.15) 25.30 21.69 34.34 — 4.82 4.82 — — 7.23 — — 1.81 Li_(1.6)Cr_(0.6)Ge_(0.3)Ti_(1.1)(PO₄)₃ 20.00 27.50 37.50 — — 7.50 — — 7.50 — — — Li_(1.9)Cr_(0.6)Ge_(0.3)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) 22.89 26.51 34.34 — — 7.23 — — 7.23 — — 1.81 Li_(1.3)Nb_(0.45)Al_(0.45)Ge_(0.2)Ti_(0.9)(PO₄)_(2.85)(BO₄)_(0.15) 17.57 24.32 38.51 — 6.08 — — — 5.41 — 6.08 2.03 LiNb_(0.3)Al_(0.3)Ge_(0.2)Ti_(1.2)(PO₄)₃ 13.51 32.43 40.54 — 4.05 — — — 5.41 — 4.05 — Li_(1.3)Fe_(0.3)Nb_(0.3)Al_(0.3)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) 17.57 29.73 38.51 — 4.05 — 4.05 — — — 4.05 2.03 Li_(1.6)Cr_(0.3)Si_(0.6)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) 19.28 26.51 34.34 — — 3.61 — 14.46 — — — 1.81 Li_(1.1)Cr_(0.1)Ge_(0.8)Ti_(1.1)(PO₄)₃ 13.75 27.50 37.50 — — 1.25 — — 20.00 — — — Li_(1.2)Cr_(0.2)Ge_(0.7)Ti_(1.1)(PO₄)₃ 15.00 27.50 37.50 — — 2.50 — — 17.50 — — — Li_(1.4)Cr_(0.4)Ge_(0.5)Ti_(1.1)(PO₄)₃ 17.50 27.50 37.50 — — 5.00 — — 12.50 — — — Li_(1.5)Cr_(0.5)Ge_(0.4)Ti_(1.1)(PO₄)₃ 18.75 27.50 37.50 — — 6.25 — — 10.00 — — — Li_(1.7)Cr_(0.7)Ge_(0.2)Ti_(1.1)(PO₄)₃ 21.25 27.50 37.50 — — 8.75 — — 5.00 — — — Li_(1.7)Cr_(0.7)Ge_(0.7)Ti_(0.6)(PO₄)₃ 21.25 15.00 37.50 — — 8.75 — — 17.50 — — — Li_(1.45)Cr_(0.45)Ge_(0.45)Ti_(1.1)(PO₄)₃ (example 5) 18.13 27.50 37.50 — — 5.63 — — 11.25 — — — Li_(1.3)Cr_(0.3)Ge_(0.5)Ti_(1.2)(PO₄)₃ 16.25 30.00 37.50 — — 3.75 — — 12.50 — — — Li_(1.6)Cr_(0.6)Ge_(0.4)Ti_(1.0)(PO₄)₃ 20.00 25.00 37.50 — — 7.50 — — 10.00 — — — Li_(1.7)Cr_(0.7)Ge_(0.4)Ti_(0.9)(PO₄)₃ 21.25 22.50 37.50 — — 8.75 — — 10.00 — — — Li_(1.8)Cr_(0.8)Ge_(0.4)Ti_(0.8)(PO₄)₃ 22.50 20.00 37.50 — — 10.00 — — 10.00 — — — Li_(1.5)Cr_(0.5)Ge_(0.3)Ti_(1.2)(PO₄)₃ 18.75 30.00 37.50 — — 6.25 — — 7.50 — — — Li_(1.5)Cr_(0.5)Ge_(0.5)Ti_(1.0)(PO₄)₃ 18.75 25.00 37.50 — — 6.25 — — 12.50 — — — Li_(1.5)Cr_(0.5)Ge_(0.7)Ti_(0.8)(PO₄)₃ 18.75 20.00 37.50 — — 6.25 — — 17.50 — — — Li_(1.5)Cr_(0.5)Ge_(0.8)Ti_(0.7)(PO₄)₃ 18.75 17.50 37.50 — — 6.25 — — 20.00 — — — Li_(1.55)Cr_(0.55)Ge_(0.35)Ti_(1.1)(PO₄)₃ 19.38 27.50 37.50 — — 6.88 — — 8.75 — — —

Compositions within the system Cr—Ge—Ti, for example, i.e., lithium-chromium-germanium-titanium phosphates, display good glass formability (i.e., a glass formability index in the range of 4-5) within the region 1-10 mol % Cr₂O₃, 5-25 mol % GeO₂, and 15-30 mol % TiO₂ (see FIG. 1). Conductivities of at least 10⁻⁴ S/cm are observed for compositions within the region 5-7 mol % Cr₂O₃, 8.5-20 mol % GeO₂ and 17-28 mol % TiO₂.

A method of making a glass-ceramic article comprises forming a glass melt including, in mole percent, 5-28% Li₂O, 14-37% TiO₂, 32-48% P₂O₅, 0-13 Al₂O₃, 0-10 Cr₂O₃, 0-13 Fe₂O₃, 0-10 Ga₂O₃, 0-5% SiO₂, 0-25 GeO₂, 0-7 V₂O₅, 0-13 Nb₂O₅, 0-17 Na₂O, 0-17 ZnO and 0-6 B₂O₃, quenching the melt to form a glass article, and heat treating the glass article to form a glass-ceramic article having an NZP phase as a majority crystalline phase.

As compared with traditional ceramic routes, i.e., powder sintering, the glass-ceramic materials made by the instant approach are fully dense. Further, the glasses can be made directly to the desired shape by casting and then then, via heat treatment, crystallized into a dense NZP glass-ceramic. Some NZP glass-ceramics are characterized by high ionic conductivity. The disclosed glass-ceramic route is more cost and time effective than traditional ceramic processing.

EXAMPLES Example 1—Li_(1.3)Nb_(0.45)Al_(0.45)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15)

Dry powders of lithium carbonate, niobium pentoxide, aluminum metaphosphate, titanium dioxide, and boric acid were mixed in a turbula mixer. The powder mix was poured into a Pt crucible and an aqueous solution of phosphoric acid was added to the dry mix and stirred to form a homogeneous slurry. The slurry was calcined overnight at 400° C. The crucible with the dried contents was then covered with a lid and placed into a furnace at 1500° C. for 3 h.

The resulting melt was poured onto a stainless steel table and roller quenched with a stainless steel roller. The sheet thickness was less than 1 mm, with ˜90% of the melt remaining glassy. The glassy parts, which had a brown color, were broken into smaller pieces and collected.

The glass pieces (about 25×25 mm) were placed onto silica disks and loaded into a box furnace for crystallization. The thermal cycle for crystallization involved heating at a rate of 10° C./min to 900° C. (hold time 2 h) and cooling at a rate of 5° C./min. After crystallization the glass-ceramic pieces were white, opaque and dense.

Conductivity was measure by gold plating both sides of an 10 mm diameter disk. The conductivity of was 1.36×10⁻⁴ S/cm.

A TGA scan, shown in FIG. 2, was performed in N₂ at 10° C./min in a Pt pan. The Li_(1.3)Nb_(0.45)Al_(0.45)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) material showed onset and peak crystallization temperatures of 664° C. and 668° C.

The x-ray analysis of the material reveals that 71% was a rhombohedral Li(Al,Nb,Ti)₂((P,B)O₃)₄ phase, 13% monoclinic Li₃(Al,X,Ti)₂(PO₄)₃, and 15% LiTi(PO₄)O.

Example 2—Li_(1.3)Cr_(0.3)Ge_(0.6)Ti_(1.1)(PO₄)₃

Dry powders of lithium carbonate, chromium(III) oxide, germanium dioxide and titanium dioxide were mixed in a turbula mixer. The powder mix was poured into a Pt crucible and an aqueous solution of phosphoric acid was added to the dry mix and stirred to form a homogeneous slurry. The slurry was calcined overnight at 400° C. The crucible with the dried contents was then covered with a lid and placed into a furnace at 1500° C. for 3 h.

The resulting melt was poured onto a stainless steel table and roller quenched with a stainless steel roller. The sheet thickness was less than 1 mm, with ˜75% of the melt remaining glassy. The glassy parts, which had a dark green color, were broken into smaller pieces and collected.

The glass pieces (about 25×25 mm) were placed onto silica disks and loaded into a box furnace for crystallization. The thermal cycle for crystallization involved heating at a rate of 10° C./min to 900° C. (hold time 2 h) and cooling at a rate of 5° C./min. After crystallization the glass-ceramic pieces were grass green, opaque and dense.

Conductivity was measure by gold plating both sides of an 8 mm diameter disk. The conductivity of was 1.99×10⁻⁵ S/cm.

A TGA scan, shown in FIG. 3, was performed in N₂ at 10° C./min in a Pt pan. The Li_(1.3)Cr_(0.3)Ge_(0.6)Ti_(1.1)(PO₄)₃ material showed onset and peak crystallization temperatures of 691° C. and 697° C.

The x-ray diffraction data are shown in FIG. 4. The primary phase (90%) is a rhombohedral Li(Cr,Ge,Ti)₂(PO₃)₄ phase. The secondary phase (10%) was LiCrP₂O₇. In addition to the sample x-ray data, also shown in FIG. 4 are the index card data for lithium germanium phosphate and lithium chromium phosphate.

An SEM micrograph of a cross-sectional fracture surface is shown in FIG. 5. The data reveal a uniform fine microstructure for Li_(1.3)Cr_(0.3)Ge_(0.6)Ti_(1.1)(PO₄)₃ crystallized at 900° C. without a discrete nucleation step.

Example 3 and 4

Li_(1.6)Cr_(0.6)Ge_(0.6)Ti_(0.8)(PO₄)₃ and Li_(1.6)Cr_(0.3)Ge_(0.6)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) compositions were prepared in a manner consistent with the synthesis of Examples 1 and 2.

Example 5—Li_(1.45)Cr_(0.45)Ge_(0.45)Ti_(1.1)(PO₄)₃

Dry powders of lithium phosphate (monobasic), chromium(III) oxide, germanium dioxide and titanium dioxide were mixed in a turbula mixer. The powder mix was poured into a Pt crucible and an aqueous solution of phosphoric acid was added to the dry mix and stirred to form a homogeneous slurry. The slurry was calcined overnight at 400° C. The crucible with the calcined contents was then covered with a lid and placed into a furnace at 1500° C. for 3 h.

The resulting melt was poured onto a stainless steel table and roller quenched with a stainless steel roller. The sheet thickness was less than 1 mm, with ˜80% of the melt remaining glassy. The glassy parts, which had a dark green color, were broken into smaller pieces and collected.

The glass pieces (about 25×25 mm) were placed onto silica disks and loaded into a box furnace for crystallization. The thermal cycle for crystallization involved heating at a rate of 10° C./min to 900° C. (hold time 2 h) and cooling at a rate of 5° C./min. After crystallization the glass-ceramic pieces were grass green, opaque and dense.

Conductivity was measure by gold plating both sides of an 8 mm diameter disk. The conductivity of was 2.41×10⁻⁴ S/cm.

A TGA scan, shown in FIG. 6, was performed in N₂ at 10° C./min in a Pt pan. The Li_(1.45)Cr_(0.45)Ge_(0.45)Ti_(1.1)(PO₄)₃ material showed onset and peak crystallization temperatures of 712° C. and 726° C.

An X-ray diffraction trace is shown in FIG. 7. The primary (90%) glass-ceramic phase indexes to Li_(1.45)Cr_(0.45)Ge_(0.45)Ti_(1.1)(PO₄)₃. The secondary (10%) phase was LiCrP₂O₇.

Example 6—Stability Evaluation

The water stability of Examples 1-4 was evaluated by measuring weight loss as a function of exposure (submersion) in de-ionized water at room temperature for up to 168 h (1 week). Weight loss as a function of time is shown in FIG. 8.

The compositions of Examples 1-3 (Li_(1.3)Nb_(0.45)Al_(0.45)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15), Li_(1.3)Cr_(0.3)Ge_(0.6)Ti_(1.1)(PO₄)₃ and Li_(1.6)Cr_(0.6)Ge_(0.6)Ti_(0.8)(PO₄)₃) displayed good stability out to 168 h. The boron-free and chromium-containing Example 3 showed a maximum weight less of less than 1%, while the boron-containing and chromium-containing Example 4 (Li_(1.6)Cr_(0.3)Ge_(0.6)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15)) had a weight loss of greater than 12% at about 25 h. It will be appreciated that the inclusion of boron in the compositions does not per se increase the water solubitity. Example 1 exhibited demonstrably good water stability as compared with Example 4, though both included equivalent amounts of BO₄.

The thermal history and select properties of exemplary compositions are given in Table 2. The glass formability of the compositions upon roller quenching is measured on a scale from 0 to 5, where a glass formability index of 0 corresponds to substantially no glass content (i.e., fully crystalline) following quenching and a glass formability index of 5 corresponds to a completely glassy or substantially completely glassy roller-quenched sheet.

A glass characterized by a glass formability index of 5 includes 85 to 100 vol. % glassy phase. A glass formability index of 4 corresponds to a roller quenched glass having from 65% up to 85 vol. % glassy phase. A glass formability index of 3 corresponds to a roller quenched sample having from 40% up to 65 vol. % glassy phase. A glass formability index of 2 corresponds to a roller quenched sample having from 15% up to 40 vol. % glassy phase. A glass formability index of 1 corresponds to a roller quenched sample having from 5% up to 15 vol. % glassy phase. A glass formability index of 0 corresponds to a roller quenched sample having less than 5 vol. % glassy phase.

The heat treatment data include both the nucleation temperature and time (T/t) and the crystallization temperature and time. The conductivity listed is that of the glass-ceramic formed using the reported heat treatment. The glass-ceramics disclosed herein may have a lithium ion conductivity of at least 1×10⁻⁴ S/cm.

The glass transition temperature (T_(g)) and crystallization peak temperature (T_(x)) of the parent glass are also listed.

TABLE 2 Thermal history and properties of glass and glass-ceramic compositions. Heat treatment Glass nucleation T t Conductivity formability T/t [° C.]/[h] [° C.] [h] [S/cm] T_(g) [° C.] T_(x) [° C.] Zn_(0.25)Li_(0.5)Fe_(0.7)Nb_(0.7)Ti_(0.6)(PO₄)₃ 4 525/1 800 2 1.0E−06 LiFe_(0.7)Nb_(0.7)Ti_(0.6)(PO₄)₃ 3 525/1 800 2 2.0E−07 Zn_(0.15)LiFe_(0.3)Nb_(0.3)Al_(0.3)Ti_(1.1)(PO₄)₃ 3 550 800 2 1.0E−07 629 Zn_(0.25)Li_(0.8)Fe_(0.3)Nb_(0.3)Al_(0.3)Ti_(1.1)(PO₄)₃ 3 550 800 2 1.0E−07 635 Li_(1.3)Nb_(0.3)Al_(0.6)Ti_(1.1)(PO₄)₃ 4 658 Zn_(0.15)LiNb_(0.3)Al_(0.6)Ti_(1.1)(PO₄)₃ 5 550 800 2 3.2E−07 663 Zn_(0.25)Li_(0.8)Nb_(0.3)Al_(0.6)Ti_(1.1)(PO₄)₃ 4 550 800 2 8.5E−07 675 Zn_(0.4)LiAl_(0.8)Ti_(1.2)(PO₄)₃ 4 550 800 2 1.7E−06 621 Zn_(0.3)LiCr_(0.3)Al_(0.3)Ti_(1.4)(PO₄)₃ 3 550 800 2 5.3E−07 672 Zn_(0.3)Li_(1.3)Fe_(0.3)Al_(0.6)Ti_(1.1)(PO₄)₃ 3 900 2 4.2E−06 581 Li_(1.3)Cr_(0.3)Nb_(0.3)Al_(0.3)Ti_(1.1)(PO₄)₃ 3 678/1 900 6 2.2E−05 714 LiNb_(0.45)Al_(0.45)Ti_(1.1)(PO₄)₃ 5 676/1 900 2 1.6E−05 623 721 Li_(0.95)Nb_(0.4)Al_(0.35)Ti_(1.25)(PO₄)₃ 3 900 2 9.2E−07 704 LiNb_(0.6)Al_(0.6)Ti_(0.8)(PO₄)₃ 4 900 2 1.5E−05 616 697 Li_(1.6)Fe_(0.3)Nb_(0.3)Al_(0.6)Ti_(0.8)(PO₄)₃ 4 558/1 700 2 7.8E−07 533 592 Li_(1.3)V_(0.3)Al_(0.6)Ti_(1.1)(PO₄)₃ 3 900 2 1.1E−05 564 626 Li_(0.7)V_(0.3)Nb_(0.3)Al_(0.3)Ti_(1.1)(PO₄)₃ 4 645/1 900 2 4.9E−07 717 Li_(1.3)Nb_(0.45)Al_(0.45)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) 4 900 2 1.4E−04 597 668 (example 1) Li_(1.6)Nb_(0.45)Al_(0.45)Ti_(1.1)(PO₄)_(2.7)(BO₄)_(0.3) 5 611 900 2 6.9E−06 570 646 Li_(1.3)Cr_(0.3)Ge_(0.6)Ti_(1.1)(PO₄)₃ (example 2) 4 900 2 4.8E−05 625 697 Li_(1.3)Cr_(0.3)Ge_(0.9)Ti_(0.8)(PO₄)₃ 5 900 2 2.0E−05 605 701 Li_(1.4)Fe_(0.3)Nb_(0.3)Al_(0.4)Ti_(1.0)(PO₄)₃ 3 500/1 900 3 9.3E−07 567 614 Li_(1.4)Fe_(0.4)Nb_(0.4)Al_(0.4)Ti_(0.8)(PO₄)₃ 3 500/1 900 3 5.0E−07 537 607 Li_(1.6)Cr_(0.6)Ge_(0.6)Ti_(0.8)(PO₄)₃ (example 3) 4 900 2 9.3E−05 653 733 Li_(1.6)Cr_(0.3)Ge_(0.6)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) 4 500/1 900 2 2.8E−04 622 681 (example 4) Li_(1.4)Cr_(0.4)Ge_(0.4)Ti_(1.2)(PO₄)₃ 3 500/1 900 2 1.3E−05 622 675 Li_(1.6)Cr_(0.3)Al_(0.3)Ge_(0.3)Ti_(1.1)(PO₄)₃ 4 500/1 900 2 8.5E−05 646 687 LiNb_(0.45)Al_(0.45)Ge_(0.2)Ti_(0.9)(PO₄)₃ 5 900 2 1.4E−04 550 637 Li_(1.9)Cr_(0.6)Ge_(0.6)Ti_(0.8)(PO₄)_(2.85)(BO₄)_(0.15) 3 900 2 2.4E−05 613 705 Li_(1.6)Cr_(0.6)Si_(0.1)Ti_(1.3)(PO₄)₃ 3 900 2 7.0E−06 651 742 Li_(1.9)Cr_(0.6)Si_(0.1)Ti_(1.3)(PO₄)_(2.85)(BO₄)_(0.15) 3 900 2 1.7E−04 724 Li_(1.9)Cr_(0.3)Al_(0.3)Ge_(0.3)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) 3 900 2 5.8E−05 573 664 Li_(1.8)Cr_(0.4)Al_(0.4)Ge_(0.3)Ti_(0.9)(PO₄)₃ 4 900 2 2.7E−05 594 684 Li_(2.1)Cr_(0.4)Al_(0.4)Ge_(0.3)Ti_(0.9)(PO₄)_(2.85)(BO₄)_(0.15) 4 900 2 1.7E−06 577 665 Li_(1.6)Cr_(0.6)Ge_(0.3)Ti_(1.1)(PO₄)₃ 3 900 2 1.0E−05 654 730 Li_(1.9)Cr_(0.6)Ge_(0.3)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) 3 900 2 2.5E−10 620 695 Li_(1.3)Nb_(0.45)Al_(0.45)Ge_(0.2)Ti_(0.9)(PO₄)_(2.85)(BO₄)_(0.15) 4 5.19E−05  591 677 LiNb_(0.3)Al_(0.3)Ge_(0.2)Ti_(1.2)(PO₄)₃ 4 1.09E−06  639 705 Li_(1.3)Fe_(0.3)Nb_(0.3)Al_(0.3)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) 3 1.30E−06  569 631 Li_(1.6)Cr_(0.3)Si_(0.6)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) 5 4.44E−06  673 Li_(1.1)Cr_(0.1)Ge_(0.8)Ti_(1.1)(PO₄)₃ 3 1.13E−05  629 699 Li_(1.2)Cr_(0.2)Ge_(0.7)Ti_(1.1)(PO₄)₃ 4 2.98E−05  635 715 Li_(1.4)Cr_(0.4)Ge_(0.5)Ti_(1.1)(PO₄)₃ 4 7.15E−05  633 718 Li_(1.5)Cr_(0.5)Ge_(0.4)Ti_(1.1)(PO₄)₃ 5 3.12E−04  604 728 Li_(1.7)Cr_(0.7)Ge_(0.2)Ti_(1.1)(PO₄)₃ 3 3.21E−05  670 739 Li_(1.7)Cr_(0.7)Ge_(0.7)Ti_(0.6)(PO₄)₃ 5 6.05E−05  628 739 Li_(1.45)Cr_(0.45)Ge_(0.45)Ti_(1.1)(PO₄)₃ (example 5) 4 2.41E−04  648 726 Li_(1.3)Cr_(0.3)Ge_(0.5)Ti_(1.2)(PO₄)₃ 3 3.83E−05  652 716 Li_(1.6)Cr_(0.6)Ge_(0.4)Ti_(1.0)(PO₄)₃ 3 8.20E−06  642 725 Li_(1.7)Cr_(0.7)Ge_(0.4)Ti_(0.9)(PO₄)₃ 3 3.08E−06  657 734 Li_(1.8)Cr_(0.8)Ge_(0.4)Ti_(0.8)(PO₄)₃ 3 1.83E−05  652 741 Li_(1.5)Cr_(0.5)Ge_(0.3)Ti_(1.2)(PO₄)₃ 3 5.83E−06  645 719 Li_(1.5)Cr_(0.5)Ge_(0.5)Ti_(1.0)(PO₄)₃ 4 1.47E−04  643 721 Li_(1.5)Cr_(0.5)Ge_(0.7)Ti_(0.8)(PO₄)₃ 4 1.45E−04  636 720 Li_(1.5)Cr_(0.5)Ge_(0.8)Ti_(0.7)(PO₄)₃ 3 1.06E−04  645 724 Li_(1.55)Cr_(0.55)Ge_(0.35)Ti_(1.1)(PO₄)₃ 3 1.55E−04  633 720

Crystallographic data for the glass-ceramic materials are summarized in Table 3.

TABLE 3 Crystallographic properties of glass-ceramic compositions rhombohedral phase [%] a [nm] c [nm] Zn_(0.25)Li_(0.5)Fe_(0.7)Nb_(0.7)Ti_(0.6)(PO₄)₃ LiFe_(0.7)Nb_(0.7)Ti_(0.6)(PO₄)₃ Zn_(0.15)LiFe_(0.3)Nb_(0.3)Al_(0.3)Ti_(1.1)(PO₄)₃ 99 8.5189 20.991 Zn_(0.25)Li_(0.8)Fe_(0.3)Nb_(0.3)Al_(0.3)Ti_(1.1)(PO₄)₃ 92 8.5289 21.061 Li_(1.3)Nb_(0.3)Al_(0.6)Ti_(1.1)(PO₄)₃ 99 8.4929 20.8941 Zn_(0.15)LiNb_(0.3)Al_(0.6)Ti_(1.1)(PO₄)₃ 86 8.5145 20.9407 Zn_(0.25)Li_(0.8)Nb_(0.3)Al_(0.6)Ti_(1.1)(PO₄)₃ 82 8.5235 21.005 Zn_(0.4)LiAl_(0.8)Ti_(1.2)(PO₄)₃ 69 8.4819 20.834 Zn_(0.3)LiCr_(0.3)Al_(0.3)Ti_(1.4)(PO₄)₃ 8.5018 20.8811 Zn_(0.3)Li_(1.3)Fe_(0.3)Al_(0.6)Ti_(1.1)(PO₄)₃ 71 8.5024 20.931 Li_(1.3)Cr_(0.3)Nb_(0.3)Al_(0.3)Ti_(1.1)(PO₄)₃ 82 8.5162 20.9521 LiNb_(0.45)Al_(0.45)Ti_(1.1)(PO₄)₃ 88 8.5017 20.9558 Li_(0.95)Nb_(0.4)Al_(0.35)Ti_(1.25)(PO₄)₃ 53 8.503 21.023 LiNb_(0.6)Al_(0.6)Ti_(0.8)(PO₄)₃ 98 8.5087 21.032 Li_(1.6)Fe_(0.3)Nb_(0.3)Al_(0.6)Ti_(0.8)(PO₄)₃ 59 8.5082 20.999 Li_(1.3)V_(0.3)Al_(0.6)Ti_(1.1)(PO₄)₃ 78 8.4599 20.786 Li_(0.7)V_(0.3)Nb_(0.3)Al_(0.3)Ti_(1.1)(PO₄)₃ 76 8.5213 21.086 Li_(1.3)Nb_(0.45)Al_(0.45)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) 71 8.4964 20.9045 (example 1) Li_(1.6)Nb_(0.45)Al_(0.45)Ti_(1.1)(PO₄)_(2.7)(BO₄)_(0.3) 37 8.4935 20.587 Li_(1.3)Cr_(0.3)Ge_(0.6)Ti_(1.1)(PO₄)₃ 91 8.4338 20.7689 (example 2) Li_(1.3)Cr_(0.3)Ge_(0.9)Ti_(0.8)(PO₄)₃ 88 8.3909 20.7361 Li_(1.4)Fe_(0.3)Nb_(0.3)Al_(0.4)Ti_(1.0)((PO₄)₃ 72 8.52125 20.9194 Li_(1.4)Fe_(0.4)Nb_(0.4)Al_(0.4)Ti_(0.8)(PO₄)₃ 73 8.5327 20.9841 Li_(1.6)Cr_(0.6)Ge_(0.6)Ti_(0.8)(PO₄)₃ 74 8.4372 20.865 (example 3) Li_(1.6)Cr_(0.3)Ge_(0.6)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) 78 8.46712 20.8045 (example 4) Li_(1.4)Cr_(0.4)Ge_(0.4)Ti_(1.2)(PO₄)₃ 83 8.468 20.857 Li_(1.6)Cr_(0.3)Al_(0.3)Ge_(0.3)Ti_(1.1)(PO₄)₃ 79 8.4559 20.7978 LiNb_(0.45)Al_(0.45)Ge_(0.2)Ti_(0.9)(PO₄)₃ 84 8.39563 20.6508 Li_(1.9)Cr_(0.6)Ge_(0.6)Ti_(0.8)(PO₄)_(2.85)(BO₄)_(0.15) 76 8.3727 21.4079 Li_(1.6)Cr_(0.6)Si_(0.1)Ti_(1.3)(PO₄)₃ 57 8.485 21.189 Li_(1.9)Cr_(0.6)Si_(0.1)Ti_(1.3)(PO₄)_(2.85)(BO₄)_(0.15) 98 8.486 21.341 Li_(1.9)Cr_(0.3)Al_(0.3)Ge_(0.3)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) 81 Li_(1.8)Cr_(0.4)Al_(0.4)Ge_(0.3)Ti_(0.9)(PO₄)₃ 79 8.397 21.326 Li_(2.1)Cr_(0.4)Al_(0.4)Ge_(0.3)Ti_(0.9)(PO₄)_(2.85)(BO₄)_(0.15) 77 8.383 21.602 Li_(1.6)Cr_(0.6)Ge_(0.3)Ti_(1.1)(PO₄)₃ 70 8.464 21.257 Li_(1.9)Cr_(0.6)Ge_(0.3)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) 82 8.456 21.364 Li_(1.3)Nb_(0.45)Al_(0.45)Ge_(0.2)Ti_(0.9)(PO₄)_(2.85)(BO₄)_(0.15) 98.4 8.49 20.97 LiNb_(0.3)Al_(0.3)Ge_(0.2)Ti_(1.2)(PO₄)₃ 100 8.4809 20.9277 Li_(1.3)Fe_(0.3)Nb_(0.3)Al_(0.3)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) 100 8.52607 20.9291 Li_(1.6)Cr_(0.3)Si_(0.6)Ti_(1.1)(PO₄)_(2.85)(BO₄)_(0.15) 100 8.50379 20.9351 Li_(1.1)Cr_(0.1)Ge_(0.8)Ti_(1.1)(PO₄)₃ 96 8.40972 20.7612 Li_(1.2)Cr_(0.2)Ge_(0.7)Ti_(1.1)(PO₄)₃ 92 8.41757 20.7879 Li_(1.4)Cr_(0.4)Ge_(0.5)Ti_(1.1)(PO₄)₃ 89 8.44437 20.8261 Li_(1.5)Cr_(0.5)Ge_(0.4)Ti_(1.1)(PO₄)₃ 88 8.4569 20.8598 Li_(1.7)Cr_(0.7)Ge_(0.2)Ti_(1.1)(PO₄)₃ Li_(1.7)Cr_(0.7)Ge_(0.7)Ti_(0.6)(PO₄)₃ Li_(1.45)Cr_(0.45)Ge_(0.45)Ti_(1.1)(PO₄)₃ 90 8.4501 20.8343 (example 5) Li_(1.3)Cr_(0.3)Ge_(0.5)Ti_(1.2)(PO₄)₃ 90 8.4434 20.8073 Li_(1.6)Cr_(0.6)Ge_(0.4)Ti_(1.0)(PO₄)₃ 88 8.457 20.860 Li_(1.7)Cr_(0.7)Ge_(0.4)Ti_(0.9)(PO₄)₃ 87 8.454 20.850 Li_(1.8)Cr_(0.8)Ge_(0.4)Ti_(0.8)(PO₄)₃ 85 8.453 20.825 Li_(1.5)Cr_(0.5)Ge_(0.3)Ti_(1.2)(PO₄)₃ 91 8.472 20.875 Li_(1.5)Cr_(0.5)Ge_(0.5)Ti_(1.0)(PO₄)₃ 90 8.441 20.845 Li_(1.5)Cr_(0.5)Ge_(0.7)Ti_(0.8)(PO₄)₃ 89 8.414 20.799 Li_(1.5)Cr_(0.5)Ge_(0.8)Ti_(0.7)(PO₄)₃ 91 8.461 20.879 Li_(1.55)Cr_(0.55)Ge_(0.35)Ti_(1.1)(PO₄)₃ 89 8.397 20.785

Embodiments relate to a glass-ceramic solid electrolyte. The glass-ceramic may have a lithium ion conductivity of at least 1×10⁻⁴ S/cm. The solid electrolyte may be incorporated into an energy storage device such as a fuel cell or a lithium-ion battery.

As used herein, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a “glass” includes examples having two or more such “glasses” unless the context clearly indicates otherwise.

Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, examples include from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that any particular order be inferred.

It is also noted that recitations herein refer to a component being “configured” or “adapted to” function in a particular way. In this respect, such a component is “configured” or “adapted to” embody a particular property, or function in a particular manner, where such recitations are structural recitations as opposed to recitations of intended use. More specifically, the references herein to the manner in which a component is “configured” or “adapted to” denotes an existing physical condition of the component and, as such, is to be taken as a definite recitation of the structural characteristics of the component.

While various features, elements or steps of particular embodiments may be disclosed using the transitional phrase “comprising,” it is to be understood that alternative embodiments, including those that may be described using the transitional phrases “consisting” or “consisting essentially of,” are implied. Thus, for example, implied alternative embodiments to a glass or glass-ceramic composition that comprises particular constituents include embodiments where the composition consists of the constituents and embodiments where the composition consists essentially of the constituents.

It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit and scope of the invention. Since modifications, combinations, sub-combinations and variations of the disclosed embodiments incorporating the spirit and substance of the invention may occur to persons skilled in the art, the invention should be construed to include everything within the scope of the appended claims and their equivalents. 

We claim:
 1. A glass-ceramic having a composition comprising, in mole percent: 5-28% Li₂O, 14-37% TiO₂, and 32-48% P₂O₅, and further comprising at least one relationship (i)-(iii), wherein (i) the composition comprises at least two oxides selected from the group consisting of >0-13% Al₂O₃, >0-13% Fe₂O₃ and >0-13% Nb₂O₅; (ii) the composition comprises at least two oxides selected from the group consisting of >0-10% Cr₂O₃, >0-5% SiO₂ and >0-25% GeO₂; and (iii) the composition comprises at least three oxides selected from the group consisting of >0-13% Al₂O₃, >0-13% Fe₂O₃; >0-13% Nb₂O₅, >0-10% Cr₂O₃, >0-5% SiO₂ and >0-25% GeO₂; and wherein the glass-ceramic comprises at least 70 vol % of a NZP crystalline phase and a lithium ion conductivity of at least 1×10⁻⁴ S/cm.
 2. The glass-ceramic according to claim 1, comprising 4-10% Al₂O₃ and 4-10% Nb₂O₅.
 3. The glass-ceramic according to claim 1, further comprising 1-4% B₂O₃.
 4. The glass-ceramic according to claim 1, comprising 4-10% Al₂O₃, 4-10% Nb₂O₅ and 1-4% B₂O₃.
 5. The glass-ceramic according to claim 1, comprising 1-8% Cr₂O₃ and 4-20% GeO₂.
 6. The glass-ceramic according to claim 1, further comprising at least one oxide selected from the group consisting of >0-17% Na₂O and >0-17% ZnO.
 7. A glass-ceramic article having a NZP crystalline phase characterized by the formula M_(y)A₂(XO₄)₃, (0.1≤y≤2.2) where M represents one or more monovalent or divalent cations selected from the group consisting of Li, Na and Zn, A represents one or more trivalent, tetravalent or pentavalent cations selected from the group consisting of Al, Cr, Fe, Ga, Si, Ti, Ge, V and Nb, and X represents P cations which may be partially substituted by B cations, and further comprising at least one relationship (i)-(iii), wherein (i) A represents two or more cations selected from the group consisting of Al, Fe and Nb; and (ii) A represents two or more cations selected from the group consisting of Cr, Si and Ge; and (iii) A represents three or more cations selected from the group consisting of Al, Fe, Nb, Cr, Si and Ge; and wherein the glass-ceramic article comprises at least 70 vol % of the NZP crystalline phase and a lithium ion conductivity of at least 1×10⁻⁴ S/cm.
 8. The glass-ceramic article according to claim 7, wherein M represents Li and Zn.
 9. The glass-ceramic article according to claim 7, wherein A represents Al, Ti and Nb.
 10. The glass-ceramic article according to claim 7, wherein A represents Cr, Ti and Ge.
 11. The glass-ceramic article according to claim 7, wherein A represents three or more cations selected from the group consisting of Al, Cr, Fe, Ga, Si, Ti, Ge, V and Nb.
 12. The glass-ceramic article according to claim 7, wherein X represents P and B.
 13. The glass-ceramic article according to claim 7, comprising 4-10 mol. % Al₂O₃ and 4-10 mol. % Nb₂O₅.
 14. The glass-ceramic article according to claim 7, comprising 1-4 mol. % B₂O₃.
 15. The glass-ceramic article according to claim 7, comprising 4-10 mol. % Al₂O₃, 4-10 mol. % Nb₂O₅ and 1-4 mol. % B₂O₃.
 16. The glass-ceramic article according to claim 7, comprising 1-8 mol. % Cr₂O₃ and 4-20 mol. % GeO₂.
 17. The glass-ceramic article according to claim 7, wherein the glass-ceramic article comprises less than 1 vol % of glassy phase.
 18. The glass-ceramic article according to claim 7, wherein the article has a thickness of less than 2 mm.
 19. The glass-ceramic article according to claim 7, wherein M is Li and 1.2≤y≤2.2.
 20. A glass-ceramic comprising at least 70 vol % of a NZP crystalline phase and having a composition comprising, in mole percent: 5-28% Li₂O, 14-37% TiO₂, 32-48% P₂O₅, and at least one oxide selected from the group consisting of >0-17% Na₂O and >0-17% ZnO, and further comprising at least one relationship (i)-(iv), wherein (i) the composition comprises at least two oxides selected from the group consisting of >0-13% Al₂O₃, >0-13% Fe₂O₃ and >0-13% Nb₂O₅; (ii) the composition comprises at least two oxides selected from the group consisting of >0-10% Cr₂O₃, >0-5% SiO₂ and >0-25% GeO₂; (iii) the composition comprises at least three oxides selected from the group consisting of >0-13% Al₂O₃, >0-13% Fe₂O₃; >0-13% Nb₂O₅, >0-10% Cr₂O₃ and >0-25% GeO₂; and (iv) the composition comprises at least three oxides selected from the group consisting of >0-13% Fe₂O₃; >0-13% Nb₂O₅, >0-10% Cr₂O₃, >0-5% SiO₂ and >0-25% GeO₂.
 21. The glass-ceramic according to claim 20, wherein the glass-ceramic comprises less than 5 vol % of glassy phase. 